CN108325548A - A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas - Google Patents
A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas Download PDFInfo
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- CN108325548A CN108325548A CN201810212023.7A CN201810212023A CN108325548A CN 108325548 A CN108325548 A CN 108325548A CN 201810212023 A CN201810212023 A CN 201810212023A CN 108325548 A CN108325548 A CN 108325548A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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Abstract
The present invention relates to a kind of preparation methods of low carbon alcohol by synthetic gas molybdenum sulphide, include the following steps:（1）By four hydration ammonium heptamolybdates and thiocarbamide according to molar ratio Mo:S=1:24 are added to the water, and solution A is made after dissolving；（2）Solution A is added in hydrothermal reaction kettle, 220 DEG C of reactions, product is washed, dry, obtains sediment A, i.e. petal-shaped MoS2；（3）By sediment A and potassium carbonate according to molar ratio Mo:K=1:0.5 1 mechanical lappings are up to low carbon alcohol by synthetic gas catalyst.The catalyst has preparation method simple, and sulfur resistance is good, the total alcohol of product, C2+The advantages that alcohol high selectivity, has good prospects for commercial application.
Description
Technical field
The present invention relates to technical field of chemical engineering catalysts, are specifically related to a kind of vulcanization molybdenum base for low carbon alcohol by synthetic gas
Method for preparing catalyst and reaction condition preparing molybdenum sulphide more particularly, to one kind with hydrothermal synthesis method.
Background technology
Energy shortage and environmental degradation are the significant problems that current mankind faces.With the increasingly consumption of petroleum resources, open
" green energy resource " of hair high-efficiency cleaning not only has broad application prospects, and has very great strategic importance.Wherein,
It is energy resources cleaning to generate synthesis gas to prepare clean fuel liquid and other high valuable chemicals via coal or biomass
The important channel efficiently utilized.
Currently, the vehicle-use alcohol gasoline (E10) of China's sale, is as added 10%（Volume fraction）Fuel ethanol tune
Gasoline made of conjunction.It is restricted by raw material supply and production cost, cannot be satisfied as the ethyl alcohol that raw material produces using grain and constantly increase
Industrial alcohol and alcohol fuel consumption demand.Novel non-grain ethyl alcohol technology, including acetic acid（Acetate）Preparation of ethanol by hydrogenating, fiber
Element ethyl alcohol, synthesis gas ethyl alcohol etc. will impact traditional grain ethyl alcohol technology, and change is brought for ethyl alcohol industry.According to statistics,
The yield of Chinese gasoline in 2016 is 129,320,000 tons.It is added according to national regulation 10%, alcohol fuel demand is 1293.2 ten thousand tons,
Consider the output of bioanalysis ethyl alcohol（More than 200 ten thousand tons of annual output）, synthesis gas preparing fuel ethanol has about 10,000,000 tons of market empty
Between.China is synthesis gas ethyl alcohol band with the limited deliverability of alcohol fuel to the huge potential consumption demand of alcohol fuel
The larger market opportunity is carried out.
It is the heat subject of domestic and international scientific research department from the direct synthesizing alcohol of synthesis gas, there are many achievements, but not industrial
Change.Critical issue be there is presently no one highly selective, high activity, high stability and catalyst cheap and easy to get be suitable for it is big
Technical scaleization is run.Currently, the research of low carbon alcohol by synthetic gas catalyst is concentrated mainly on noble metal rhodium base catalyst, modification
Fischer-tropsch catalysts, modified methanol catalyst and modified catalyst with base of molybdenum.Although the alcohols selectivity of rhodium base catalyst is higher,
It is expensive since rhodium is noble metal, be not suitable for industrialized production.Although modified Fischer-Tropsch catalyst and modified methanol catalyst tool
Have the advantages that reaction condition is mild, but by often containing S elements in the synthesis gas of Coal Gasification production, it is toxic to catalyst to be turned into
With, and production cost can be further increased to synthetic gas desulfurization.The molybdenum sulfide of modified catalyst with base of molybdenum, especially alkali modification is urged
Agent has good sulfur resistance, and alcohols selectivity is higher, and there are potential research and development to be worth.The Dow Chemical in the U.S.
Company reported application of the molybdenum sulphide in low carbon alcohol by synthetic gas for the first time in 1987 in the patent of its application,
The catalyst system and catalyzing has good sulfur resistance, and low-carbon alcohols product water content is few, C2+Alcohol selectivity is higher.The country is about synthesis gas
The patent of low-carbon alcohols molybdenum sulphide processed is less, it can be mentioned that Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences
Sun Yuhan seminars obtain the synthesis gas system of function admirable by the way that the auxiliary agents such as Ni, Fe, Mn, K are added into molybdenum sulfide catalyst
Low-carbon alcohol catalyst, total alcohol selectivity is up to 60% or more.Only drawback is that the catalyst system and catalyzing primary product is methanol.Tradition
The molybdenum sulphide for preparing of pyrolysismethod due to passing through high-temperature roasting, cause catalytic active site less, activity is relatively low.Via
Molybdenum sulfide crystallinity prepared by hydrothermal synthesis is relatively low, and lamella is relatively thin, is conducive to expose more catalytic active sites, it is possible that right
Low carbon alcohol by synthetic gas has higher catalytic activity.
Invention content
Present invention aims at providing a kind of novel processing step of low carbon alcohol by synthetic gas high performance vulcanization catalyst with base of molybdenum,
Molybdenum sulfide catalyst is prepared using hydrothermal synthesis method.The catalyst have the total alcohol selectivity of excellent low carbon alcohol by synthetic gas and
C2+Alcohol selectivity, it is of low cost, it is simple for process, there is good actual application value.
Invention is mainly including the preparation of active component molybdenum sulfide, the addition of auxiliary agent and catalyst reaction evaluation.With
Lower operating procedure and schematic illustration for the present invention:
（1）Four hydration ammonium heptamolybdates and thiocarbamide are dissolved in water, solution is transferred to the stainless steel with polytetrafluoroethylsubstrate substrate
In autoclave, reacted in 220 DEG C of thermostatic drying chambers for 24 hours, after reaction, gained sediment through being centrifuged repeatedly, washing,
After ethyl alcohol is washed, in 60 DEG C of dryings, petal-shaped MoS is obtained2Solid powder.
（2）By petal-shaped MoS2Solid powder and potassium carbonate mechanical lapping 1h, obtained solid powder are made through 12MPa tablettings
The particle of 40-60 mesh, as modified molybdenum sulphide catalyst are collected in grain, sieving.
The present invention also provides reaction condition of the catalyst in the reaction of hydrogenation synthesis alcohol.
Advantages of the present invention:
（1）Catalyst preparation process is simple, mild condition, is suitble to industrial production；
（2）The catalyst of synthesis has total alcohol high selectivity, C2+The advantages that alcohol high selectivity, sulfur resistance are good.
Description of the drawings
Fig. 1 is the XRD spectra of hydro-thermal method synthesis molybdenum sulfide
Fig. 2 is the SEM photograph of hydro-thermal method synthesis molybdenum sulfide
Fig. 3 is the HRTEM photos of hydro-thermal method synthesis molybdenum sulfide
Specific implementation mode
Embodiment 1
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.0657g thiocarbamides（Mo:S is 1:2）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
300 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 2
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.0657g thiocarbamides（Mo:S is 1:2）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
330 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 3
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.0657g thiocarbamides（Mo:S is 1:2）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
350 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 4
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
300 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 5
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
330 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 6
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
350 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 7
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 2.1314g thiocarbamides（Mo:S is 1:4）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
300 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 8
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 2.1314g thiocarbamides（Mo:S is 1:4）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
330 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 9
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 2.1314g thiocarbamides（Mo:S is 1:4）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.3g potassium carbonate
（Mo:K=1:1）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2It urges
Agent carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g are mixed
It closes 40-60 mesh quartz sands and is filled in constant temperature zone, top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
350 DEG C, pressure 10MPa, air speed 3000h-1, synthesis gas H2/CO=1:1.Reaction product uses the gas-chromatography equipped with capillary column
Analysis.Test result is listed in table 1.
Embodiment 10
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.15g potassium carbonate
（Mo:K=1:0.5）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2
Catalyst carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g,
Mixing 40-60 mesh quartz sands are filled in constant temperature zone, and top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
300 DEG C, pressure 10MPa, air speed 3000h of degree-1, synthesis gas H2/CO=1:1.Reaction product uses the gas phase color equipped with capillary column
Spectrum analysis.Test result is listed in table 1.
Embodiment 11
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.15g potassium carbonate
（Mo:K=1:0.5）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2
Catalyst carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g,
Mixing 40-60 mesh quartz sands are filled in constant temperature zone, and top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
330 DEG C, pressure 10MPa, air speed 3000h of degree-1, synthesis gas H2/CO=1:1.Reaction product uses the gas phase color equipped with capillary column
Spectrum analysis.Test result is listed in table 1.
Embodiment 12
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.15g potassium carbonate
（Mo:K=1:0.5）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2
Catalyst carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g,
Mixing 40-60 mesh quartz sands are filled in constant temperature zone, and top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
350 DEG C, pressure 10MPa, air speed 3000h of degree-1, synthesis gas H2/CO=1:1.Reaction generates product and uses the capillary column being equipped with
Gas chromatographic analysis.Test result is listed in table 1.
Embodiment 13
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.21g potassium carbonate
（Mo:K=1:0.7）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2
Catalyst carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g,
Mixing 40-60 mesh quartz sands are filled in constant temperature zone, and top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
300 DEG C, pressure 10MPa, air speed 3000h of degree-1, synthesis gas H2/CO=1:1.Reaction product uses the gas phase color equipped with capillary column
Spectrum analysis.Test result is listed in table 1.
Embodiment 14
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.21g potassium carbonate
（Mo:K=1:0.7）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2
Catalyst carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g,
Mixing 40-60 mesh quartz sands are filled in constant temperature zone, and top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
330 DEG C, pressure 10MPa, air speed 3000h of degree-1, synthesis gas H2/CO=1:1.Reaction product uses the gas phase color equipped with capillary column
Spectrum analysis.Test result is listed in table 1.
Embodiment 15
It weighs 1.2359g tetra- and is hydrated ammonium heptamolybdate and 1.5986g thiocarbamides（Mo:S is 1:3）It is dissolved in 75ml water, solution is packed into
In 100ml ptfe autoclaves, and it is sealed in stainless steel casing.220 DEG C of reactions for 24 hours, wait for cold reaction kettle in an oven
But to after room temperature, solid product is washed 3 times, and ethyl alcohol is washed 1 time, 60 DEG C of dry 12h.0.7g products are mixed with 0.21g potassium carbonate
（Mo:K=1:0.7）, mechanical lapping 1h, tabletting sieving, the catalyst of collection 40-60 mesh.K-MoS prepared by the above method2
Catalyst carries out catalytic performance test in stainless steel fixed bed reactors.Reactor inside diameter 8mm, loaded catalyst 0.4g,
Mixing 40-60 mesh quartz sands are filled in constant temperature zone, and top preheating section and lower part soaking zone load quartz sand.Reaction condition:Temperature
350 DEG C, pressure 10MPa, air speed 3000h of degree-1, synthesis gas H2/CO=1:1.Reaction product uses the gas phase color equipped with capillary column
Spectrum analysis.Test result is listed in table 1.
TableCatalyst is to low carbon alcohol by synthetic gas catalytic performance test result
As shown in Table 1, Mo when preparing molybdenum sulfide catalyst:The molar ratio of S is 1:3, Mo:The molar ratio of K is 1:0.7, reaction temperature
For CO conversion ratios up to 23.4%, total alcohol selectively reaches 75.6%, C when degree is 350 DEG C2+Alcohol high selectivity shows that this is urged up to 79.4%
Agent shows good total alcohol selectivity and C2+Alcohol selectivity, is excellent low carbon alcohol by synthetic gas catalyst.And when preparation
Mo when molybdenum sulfide catalyst:The molar ratio of S is 1:3, Mo:The molar ratio of K is 1:When 0.5, when reaction temperature is 300 DEG C, CO turns
For rate up to 14.4%, total alcohol selectively reaches 80.9%, C2+For alcohol selectivity up to 51.6%, ethyl alcohol accounts for 37.1% in total alcohol, shows this
Catalyst shows good total alcohol selectivity, C2+Alcohol selectivity and ethanol selectivity, and excellent synthesis gas ethyl alcohol are urged
Agent.
Claims (7)
1. a kind of hydro-thermal reaction preparation method of low carbon alcohol by synthetic gas molybdenum sulphide, it is characterised in that the group of catalyst
At, preparation method and reaction condition.
2. a kind of hydro-thermal reaction preparation method of low carbon alcohol by synthetic gas catalyst according to claim 1, feature exist
In including the following steps:Four hydration ammonium heptamolybdates and thiocarbamide are dissolved in water according to different proportion, solution is through hydro-thermal reaction system
Obtain petal-shaped MoS2, petal-shaped MoS2With potassium carbonate mechanical lapping according to a certain percentage, unsupported catalyst is obtained after drying.
3. according to the method described in claim 1 and 2, it is characterised in that the molybdenum source and sulphur source of catalyst raw material.
4. the wherein oxysalt of molybdenum source such as molybdenum, sulphur source such as thiocarbamide, cysteine, carbon disulfide etc., molybdenum atom and sulphur atom
Molar ratio is 1:2-4.
5. according to the method described in claim 1 and 2, it is characterised in that the method that catalyst preparation uses hydrothermal synthesis:By molybdenum
Source is dissolved in the water with sulphur source, and solution reacts in autoclave, and reaction temperature is 180-240 DEG C.
6. according to the method described in claim 1 and 2, it is characterised in that the auxiliary agent of addition be all kinds of alkali metal salts, as potassium carbonate,
Sodium carbonate, potassium acetate, cesium carbonate etc., addition K:Mo molar ratios are 0-2:1.
7. according to the method described in claim 1, it is characterized in that the use condition of catalyst be 200-400 DEG C of temperature, pressure
8-12MPa, unstripped gas V (H2)/V (CO) is 0.5-2:1, air speed 500-10000h-1。
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